TW201002165A - Copper foil for printed circuit board and copper clad laminate plate for printed circuit board - Google Patents

Copper foil for printed circuit board and copper clad laminate plate for printed circuit board Download PDF

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Publication number
TW201002165A
TW201002165A TW098118522A TW98118522A TW201002165A TW 201002165 A TW201002165 A TW 201002165A TW 098118522 A TW098118522 A TW 098118522A TW 98118522 A TW98118522 A TW 98118522A TW 201002165 A TW201002165 A TW 201002165A
Authority
TW
Taiwan
Prior art keywords
zinc
nickel
copper
layer
printed circuit
Prior art date
Application number
TW098118522A
Other languages
Chinese (zh)
Other versions
TWI452953B (en
Inventor
Terumasa Moriyama
Kengo Kaminaga
Original Assignee
Nippon Mining Co
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Filing date
Publication date
Application filed by Nippon Mining Co filed Critical Nippon Mining Co
Publication of TW201002165A publication Critical patent/TW201002165A/en
Application granted granted Critical
Publication of TWI452953B publication Critical patent/TWI452953B/en

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0239—Coupling agent for particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0355—Metal foils
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0703—Plating
    • H05K2203/0723—Electroplating, e.g. finish plating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12431—Foil or filament smaller than 6 mils
    • Y10T428/12438—Composite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12472—Microscopic interfacial wave or roughness
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12556—Organic component
    • Y10T428/12569—Synthetic resin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12583—Component contains compound of adjacent metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12583—Component contains compound of adjacent metal
    • Y10T428/1259—Oxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12611—Oxide-containing component
    • Y10T428/12618—Plural oxides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/1266—O, S, or organic compound in metal component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
    • Y10T428/12826—Group VIB metal-base component
    • Y10T428/12847—Cr-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12903—Cu-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12944—Ni-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Ceramic Engineering (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Laminated Bodies (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

Disclosed is a copper foil for a printed circuit board comprising a roughened surface of a copper foil, a layer containing nickel and zinc or compounds of nickel and zinc (hereinafter referred to as a "nickel zinc layer"), and a chromate film layer on the nickel zinc layer. The copper foil is characterized in that the weight of zinc deposited per unit area of the copper foil in the nikel zinc layer is not less than 180 μg/dm<SP>2</SP> and not more than 3500 μg/dm<SP>2</SP>, and the proportion of the weight of nickel in the plating film, i.e., {weight of nickel deposited/(weight of nickel deposited + weight of zinc deposited)} is not less than 0.38 and not more than 0.7. The above constitution can establish a surface treatment technique of a copper foil, which can effectively prevent a circuit erosion phenomenon when a copper foil is stacked on a resin base material and a circuit is subjected to soft etching with a sulfuric acid/hydrogen peroxide etching solution.

Description

201002165 六、發明說明： 【發明所屬之技術領域】 . 本發明，係關於一種耐藥品性及接著性優異之印刷電 路基板用銅箔及印刷電路基板用覆銅積層板，特別是關於 一種在銅猪之至少與樹脂的接著面，具有含有鎳與鋅或此 等化合物之層（以下，稱為「鎳辞層」。），並在該層上具有 鉻酸鹽被膜層、及進一步視需要所設之矽烷偶合劑層的印 刷電路基板用銅羯及使用該銅搭所製成之印刷電路基板用 覆銅積層板。 【先前技術】 ，半導體封裝基板騎刷電路基板之—種，係用於構裝 半導體1C晶片、其他半導體元件之印刷電路基板。形成於 半導體封裝基板之電路由於較通常之印刷電路基板微細， 因此基板材料係使用肖一般印刷電路基板不同之樹脂基 材。 半導體封裝基板，通常藉由下列步驟來製作。首先， 在高溫高壓下將銅_積層接著於合成樹脂等之基材。將此 稱為覆銅積層板或僅稱為積層板。接著，4了將作為目標 之導電性電路形成於積層板上，係藉㈣㈣性樹脂等材 :，將與電路相同之圖案印刷於銅箱上。然後，藉由敍刻 處理將所冑出之銅箱的不要部分加以去除。 飯刻後，去除印刷部而在基板上形成導電性電路。最 後將規R元件焊接於所形成之導電性電路，而形成電子 3 201002165 元件用之各種印刷電路基板。最I，與抗蚀劑或增層 (buildup)樹脂基板接合。 -般，對印刷電路基板用銅笛之品質要求，在與樹脂 基材接著之接著面（所謂粗化面）及非接著面（所謂光澤面）並 不相同，必須同時滿足兩者。 對光澤面之要求，係要求⑴外觀良好及保存時沒有氧 化變色現象’ (2)焊料潤濕性良好，（3)高溫加熱時沒有氧化 變色現象’（4)與抗蝕劑之密合性良好等。 而另一方面，對於粗化面，主要可舉出⑴在保存時沒 有氧化變色現象’（2)即使在經過高溫加熱、濕式處理、焊 接、藥品處理等後’與基材之剝離強度仍高，（3)在經過與 基材之積層、蝕刻後，沒有生成所謂積層污點等。 又，近年來隨著電路印刷圖案的微細化，亦要求銅猪 表面的低粗度化。 ^並且’於電腦或行動通訊等電子機器巾，隨著通訊之 门速 大谷量化，電氣訊號朝高頻化邁進，故要求可因 應上述需求之印刷電路基板及㈣。若電氣訊號之頻率在 1GHz以i k，貝,！電流流過導體表面之集膚效應（8他effect) 的〜a變ϋ著’而無法忽視表面之凹凸導致電流傳遞路 钇產生變化、阻抗（Impedance)變大之影響。考量此點，亦 希望銅洎之表面粗趟度小。 斤為了 口應此要求，而提出了許多對印刷電路基板用銅 箔之表面處理方法。 壓延銅箔與電解銅箔的表面處理方法有所不同，電解 4 201002165 銅箱之表面處理方法之-例如下所述。 亦即，首券 A ^ 4 Γ徒向鋼與樹脂基材之接著力（剝離強 )般係將銅與氧化銅所構成之微粒附著於銅箔表面（粗 ~里）$後為了使銅箱具有耐熱特十生，而形成黃銅或辞 等耐熱層（障壁層）。 又最後為了防止在運送時或保存時發生表面氧化等 象係知•以藉由浸潰或電解所進行之鉻酸鹽處理或電解 鋅鉻酸鹽處理等防錄處理，藉此製成製品。 其中，尤以形成耐熱層之表面處理方法為決定銅箔表 面!·生狀之重要關鍵。因Λ，形成耐熱層之金屬或合金可舉 出如Zn、Cu —Νι合金、Cu—c〇合金及Cu—Ζη合金等，而 ^ Μ Ζη &gt; Cu — Ni ^ 人人 口鱼 Cu~C〇合金及Cu—Zn合金等之 被覆層之大部分的銅&amp;已實用化（例如，參照專利文獻】）。 此等之中，形成有Cu-Zn合金（黃銅）所構成之财熱層 的銅箱使用在由環氧樹脂等所構成之印刷電路基板時，由 於具有樹脂層無污點，且經高溫保持印刷電路基板後之銅 箱的剝離強度劣化少等優異特性，因此在工業上廣為使 用。關於形成由此黃銅所構成之耐熱層的方法，詳述於專 利文獻2。 近年來，於印刷電路基板，特別是封裝基板之製造步 驟中，為了提高抗㈣或增層樹脂基板與為電路面之鋼箱 之光澤面的密合性，係使用以硫酸、過氧化氫混合液進行 軟蝕刻（soft etching)來將銅箱光澤面加以粗面化之處理。 然而’若以上述硫酸、過氧化氫混合液來對印刷電路 5 201002165 基板（係使用形成有由黄 # &amp; n &amp; 、钔所構成之耐熱層的銅箔）之銅箔 電路先澤面進行軟蝕刻， 白 Φ #丨@ 1 a务生先前所形成之電路圖宰 雨側鳊。卩（邊緣部）之侵蝕 累 ki· ^ 4-\ Ah： '路知敍）現象，而產生與樹脂美 材之剝離強度劣化的問題。 树月曰基 此電路侵蝕現象，俜… 界層，亦即露出由黃鋼所冶電路與樹脂基材之接著邊 硫酸、過氧化氯混合液所=之耐熱層的電路側面被上述 色(由黃銅所構成之故)之=的：因此導致通常應呈現黃 紅色，此部分之銅落的剝… 呈現 整個電路圖案均發生此 ^ 右 離，而成為嚴重之問題時’電路圖案將會自基材剝 ^利文獻Ν日本特公昭MW川號公報 專利文獻2:曰本特公昭54-6701號公報 【發明内容】 本發明之課題，在於開發— 化下，可提高將銅會使其他諸特性劣 路基板之銅箱的常態剝離強電 持鋇宗拄„ % 及以同酿將印刷電路板保 用作為上述電路…/ 耐熱剝離強度)，且適 勹上述電路铋蝕現象經 箔。牿別0 A 夕&amp;千导體封裝基板用的銅 J疋在於备將銅落積層於谢月t其从 剝雜；'θ土材，大幅提升耐熱 強度’且使用硫酸、過轰外_会#亡,— 餘刻時，確立可^液對電路進行軟 技術。 ⑴冷的表面處理 6 201002165 為了解決上述課題，本發明人對在銅落上進行表面處 ;之條件等㈣潛心研究的結果，發現在進行以下之銅绪 的耐熱剝離強度提升及耐硫酸、 好 W乳化虱性，亦即以硫酸、 1^氣化氫混合液所進行之銅箔井 j j /自尤澤面的軟蝕刻時，對銅箔 側之粗化面的耐侵蝕性（耐電路侵蝕性）有效。 由以上，本發明提供： υ-種印刷f路基板用㈣，係在㈣之減面 含有錄與辞或此等化合物之層（以下，稱為「錄辞層」），、以 及在δ亥層上，具備絡酸鹽被膜層，其特徵在於，該鎖鋅声 之銅箔每單位面積的鋅英 θ 曰 、 償的鮮附者重1在180#g/dm2以上、35〇〇 # g/dm以下’鍍敷被膜中 旦 鎳重里比率{鎳附著重量/(鎳附 者重1 +鋅附著重量）}在0.38以上、〇.7以下。 2)如1)所記載之印刷 荃番旦&quot;德似w 4 崎丞板用銅泊，其中，該{鎳附 者重里/(鎳附者重量+鋅著 者直里）}在0.4以上、0.55以下。 3 )如1)或2)之任—頂# — &amp; # ^ 員所5己载之印刷電路基板用銅箔， 其中，该鉻酸鹽被膜層之 。 钔泊母早位面積的鉻附著重量在 3〇#g/dm 以上' 1〇〇#g/dm2 以下。 隹 4)如1)至3)中任—項所 甘士外成 嗔所3己載之印刷電路基板用銅箔， 其中，該鎳鋅層所含有 ^ ^ ^ ^ ^ ^ 全辞中，以辞氧化物或鋅氫氧 化物之形癌存在之辞佔有45〜90%。 立中）兮鐘Μ中任—項所記載之印刷電路基板用銅箔’ 其中，該鎳鋅層所含有 仆铷夕帘能六+ 王邛鎳中，以鎳氧化物或鎳氫氧 化物之形態存在之錦佔有6〇〜8〇%。 乳 6)如1)至5)中任— $所記載之印刷電路基板用銅箔， 201002165 八中7 Γ該鉻酸鹽層上，進一步具備矽烷偶合劑層。 )士_ 1)至6)中任一項所記載之印刷電路基板用銅箔， 其中，銅箱為電解銅箱，粗化面為電錄時之粗面、或是對 此粗面進—步施以粗化處理之面、或是對電解銅箔之光澤 面施以粗化處理之面。 8)如1)至6)中任—項所記載之印刷電路基板用銅箱， :中銅泊為壓延銅箔’粗化面為對該壓延銅箔施以粗化 處理之面。 一 9)—種印刷電路基板用覆銅積層板，係將1)至8)中任 二頁所記載之印刷電路基板用銅馆與印刷電路基板用樹脂 基材加以貼合而製成。 如乂上所不，本發明之印刷電路基板用銅箱，為了不 使印刷電路基板經高溫保持後之㈣的剝離強度發生劣 化，係使用錄辞層，而並不使用被認為是以往所需要件之 由黄銅所構成的耐熱層。 藉此，可大幅地提升銅箱之耐熱剝離強度。且， 可得到能夠有效防止因藥品所造成之電路❹現象，㈣ 疋能夠提升耐硫酸、過氧化氫性之新穎的特性 電路基板用銅箱（特別是半導俨封# m 卞马印刷 1…… 疋牛導體封裝基板用銅箱)' 以及將鋼 、樹&amp;基材加以貼合所以之覆銅積層板（㈣!是半導體 封裝基板用覆銅積層板）極為有效。#然m㈣ 般之印刷電路基板用銅箔。 今 【實施方式】 8 201002165 接著，為了容易理解本發明’係具體且詳細地對本發 明進行說明。 本發明之銅箔’雖然電解銅箔及壓延鋼箔皆可使用， 但是在電解銅箔之情形時，可適用在電鍍時之粗面。又， 並且可對此粗面進一步施以粗化處理。例如，為了提升樹 脂基材與積層後之銅箱的剝離（peel)強度，係在脫脂後之銅 箔表面施以粗化處理（例如銅之「瘤」狀電沉積）的電解銅 箔，並可直接使用之。 一般，於鼓式電解銅箱製造裝置’一側（鼓側）為光澤 面，相反側則為粗面。而於壓延銅箔，則為任一側皆具有 光澤之壓延面。於本發明中，雖然電解銅箔具有粗面與光 澤面，但為粗面時，則可直接加以使用。而電解銅箔之光 澤面，為了進一步提高剝離強度，係施以粗化處理，形成 粗化面。 於壓延銅箔，亦同樣地施以粗化處理。粗化處理，無 論是何種情形，皆可使用業已公知之粗化處理，並無特別 限制。 本發明之粗化面，係指電解銅箔之電鍍時的粗面，及 施有粗化處理之電解銅箱或壓延銅落的粗化處理面，可適 用於所有之銅箔。 、首先對半‘體封裝基板用銅箔，並不設置以往即被 認為是必須之黄銅被覆層。以往，若無黄銅被覆層，雖會 擔心印刷電路基板在高溫下保持一定時間後其銅箱之制離 強度（耐熱剝離強度）會發生下降等之特性下降，但形成鎳鋅 9 201002165 層來代替黄鋼被覆層，以提升财熱剝離強度。因此，於本 考务明中，_/* 、/ 以往被認為是常識之銅箔上形成黃銅被覆 層’係重要特徵之—。 、 ^鎳鋅層，並非均勻之鎳-鋅合金，而是包含鎳及鋅之一 …為氧化物或氫氧化物I，例如’包含含有表面氧化膜 或氫氧化臈之鎳辞層者。 _ 述本發明之半導體封裝基板用銅箔，係由形成 在銅箱之粗化面(為與樹脂之接著面)的鎳鋅層、鉻酸鹽被膜 層及視需要所設之石夕烧偶合劑層所構成。銅箱，可使用上 述之壓延㈣或電解銅络。又鉻酸鹽被膜層，可使用電解 鉻酸鹽被膜層或浸潰鉻酸鹽被膜層。 發月 &gt; 上述’例如係在銅箔之粗化面，形成含有 錦與鋅或此等化合物之層(以下，稱為「鎳辞層」。），惟必 須使2上述錄鋅層之銅落每單位面積的辞附著重量在_ g 乂上35〇〇#g/dm以下。若辞附著重量未達180# g/dm，則高溫加熱後剝 雕!的另化將會加劇。又，若 鋅附著重量在3500 # g/dm2以上眛，日,— 夺則硫酸、過氧化氫系# 刻液所造成之電路端部的侵蝕將會變得顯著。 必須使{鎳附著重量/(鎳附荖 〇 L 、騍附考重置+辞附著重量）}在 U.38以上、0 7以下。若未達〇 a A · 則無法有效防止電路侵 儀現象。又，若在〇·7以上， 4熱剝離強度將會降低。 錄鋅層，通常係以下述條件央 ώ 米仟來形成。然而，只要是可 達成鎳辞層之每單位面積的辞 ,者重量在180# g/dm2以 上、3500以g/dm2以下，（鎳附 言更置/(鎳附著重量+鋅附著 10 201002165 重置）}在0·38以上、0.7以下之電鍍條件的話，則並無特別 限制’亦可使用其他的電锻條件。 (鑛敷液組成） 使 Ni . l〇g/L〜3 0g/L，Zn : lg/L〜15g/L，硫酸（H2S04): lg/L〜12g/L為基本鍍浴。 並視需要，添加氯化物離子：lg/L〜5g/L。 (電流密度）3〜40A/dm2 接著，此鉻酸鹽被膜層之製作，鉻酸鹽處理可適用電 解鉻酸鹽處理、浸潰鉻酸鹽處理、及鉻酸鹽鍍浴中含有鋅 之鋅鉻酸鹽處理。 無論是在任何一種情形，若鉻附著重量未達3〇 # g/dm2，則由於增加耐酸性與耐熱性之效果少，因此使鉻附 者重2量在30&quot;g/dm2以上。又，若鉻附著重量超過1〇〇# g/dm時，則鉻酸鹽處理之效果將會飽和，鉻附著重量無法 再增加。若總結此等，則鉻酸鹽處理層中每單位面積之鉻 附著重量較佳為3〇〜1〇〇// g/dm2。 I 用以形成上述鉻酸鹽被膜層之條件之例記載如下。然 而’如上述，並不必受到此條件之限制，業已公知之絡酸 鹽處理皆可使用。 一般，浸潰鉻酸鹽處理之情形，可達成每單位面積之 鉻附著重置30〜40/z g/dm2。X，電解鉻酸鹽處理之情形， 則可達成每單位面積之鉻附著重量3〇〜i〇〇&quot;/dm2。 此防錢處理，係會對銅箱之耐酸性與耐熱性造成影響 的因素之一，藉由鉻酸鹽處理，由於可更加提升銅箱之耐 11 201002165 藥品性與财熱性，因此為有效。 (a) 浸潰鉻酸鹽處理之一例[Technical Field] The present invention relates to a copper foil for a printed circuit board and a copper-clad laminate for a printed circuit board which are excellent in chemical resistance and adhesion, and more particularly to a copper-clad laminate. The at least the surface of the pig and the resin have a layer containing nickel and zinc or such a compound (hereinafter referred to as "nickel layer"), and have a chromate coating layer on the layer, and further optionally A copper ruthenium for a printed circuit board in which a decane coupling agent layer is provided, and a copper-clad laminate for a printed circuit board produced using the copper lap. [Prior Art] A semiconductor package substrate is a circuit board for mounting a semiconductor 1C chip or other semiconductor element. Since the circuit formed on the semiconductor package substrate is finer than the usual printed circuit board, the substrate material is a resin substrate different from the general printed circuit board. The semiconductor package substrate is usually fabricated by the following steps. First, the copper-layer is laminated to a substrate such as a synthetic resin under high temperature and high pressure. This is called a copper clad laminate or simply a laminate. Next, the target conductive circuit is formed on the laminate, and the same pattern as the circuit is printed on the copper box by means of (4) (four) resin or the like. Then, the unnecessary portion of the copper box that has been removed is removed by the etch process. After the meal, the printed portion is removed to form a conductive circuit on the substrate. Finally, the R element is soldered to the formed conductive circuit to form various printed circuit boards for the electronic 3 201002165 component. Most I, bonded to a resist or buildup resin substrate. In general, the quality requirements for the copper flute for printed circuit boards are different from those of the resin substrate (the so-called roughened surface) and the non-adhesive surface (the so-called glossy surface), and both must be satisfied. Requirements for glossy surface are required (1) good appearance and no oxidative discoloration during storage' (2) good solder wettability, (3) no oxidative discoloration when heated at high temperature' (4) adhesion to resist Good and so on. On the other hand, for the roughened surface, there are mainly (1) no oxidative discoloration during storage' (2) peeling strength with the substrate even after high-temperature heating, wet processing, welding, drug treatment, etc. High, (3) After the layering and etching with the substrate, no so-called build-up stains or the like are formed. Further, in recent years, as the circuit printing pattern is miniaturized, the surface of the copper pig is required to have a low thickness. ^And in the electronic machine towel such as computer or mobile communication, as the speed of communication is quantified, the electrical signal is moving toward high frequency, so the printed circuit board and (4) that can meet the above requirements are required. If the frequency of the electrical signal is at 1GHz with i k, Bay,! The current flowing through the surface of the conductor (the effect of the 8a effect) becomes abundance, and the unevenness of the surface cannot be ignored, resulting in a change in the current transmission path and an increase in the impedance (Impedance). Considering this point, I also hope that the surface of the matte is small. In order to meet this requirement, a number of surface treatment methods for copper foil for printed circuit boards have been proposed. The surface treatment method of the rolled copper foil and the electrolytic copper foil is different, and the surface treatment method of the electrolysis 4 201002165 copper box is as follows. That is, the first coupon A ^ 4 gangster attached the copper and copper oxide particles to the surface of the copper foil (thickness) after the adhesion of the steel to the resin substrate (peeling strong). It has a heat-resistant speciality and forms a heat-resistant layer (barrier layer) such as brass or rhodium. Finally, in order to prevent surface oxidation during transportation or storage, it is known that the product is formed by an anti-recording treatment such as chromate treatment or electrolytic zinc chromate treatment by dipping or electrolysis. Among them, the surface treatment method for forming a heat-resistant layer is an important factor for determining the surface of the copper foil! Λ Λ & & & & Cu 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成A large amount of copper &amp; of a coating layer such as an alloy or a Cu-Zn alloy has been put into practical use (for example, see Patent Document). Among these, a copper case in which a heat-generating layer composed of a Cu-Zn alloy (brass) is formed is used in a printed circuit board made of an epoxy resin or the like, and has a resin layer free from stains and is maintained at a high temperature. Since the copper case after the printed circuit board has excellent characteristics such as poor deterioration in peel strength, it is widely used industrially. A method of forming a heat-resistant layer composed of the brass is described in detail in Patent Document 2. In recent years, in the manufacturing steps of a printed circuit board, particularly a package substrate, in order to improve the adhesion of the (4) or build-up resin substrate to the shiny side of the steel box for the circuit surface, a mixture of sulfuric acid and hydrogen peroxide is used. The liquid is subjected to soft etching to roughen the shiny surface of the copper box. However, if the above-mentioned sulfuric acid or hydrogen peroxide mixed solution is used, the copper foil circuit of the printed circuit 5 201002165 substrate (using a copper foil formed of a heat-resistant layer composed of yellow # &amp; n &amp; Perform a soft etch, white Φ #丨@ 1 a. The erosion of the 卩 (edge portion) is a problem of ki· ^ 4-\ Ah: 'Lu Zhixuan', which causes deterioration of the peel strength with the resin material. The circuit is eroded by the circuit, 俜... The boundary layer, that is, the side of the circuit that exposes the heat-resistant layer of the mixture of sulfuric acid and chlorine peroxide on the circuit of the steel and the resin substrate, is the above color. The reason why brass is composed of: = so the result should usually be yellow-red, this part of the copper peeling... This is the entire circuit pattern that appears to be right, and when it becomes a serious problem, the circuit pattern will be OBJECTS OF THE EMBODIMENT OF THE INVENTION OBJECTS OF THE INVENTION The present invention is directed to the development of the present invention. The normal peeling of the copper box of the inferior substrate is the same as that of the above-mentioned circuit.../heat-resistant peeling strength, and it is suitable for the above-mentioned circuit corrosion phenomenon. 0 A 夕 & Thousand-conductor package substrate copper J 疋 lies in the preparation of the copper layer deposited in Xie Yue t from the stripping; 'θ soil material, greatly improve the heat resistance ' and use sulfuric acid, over the bomb outside _ will # Death, - when you are in the moment, you can establish the liquid into the circuit. (1) Cold surface treatment 6 201002165 In order to solve the above problems, the present inventors have found that the surface of the copper drop is subjected to the conditions of the fourth (4) research, and it has been found that the heat-resistant peel strength of the following copper is improved. Resistance to sulfuric acid, good emulsification, that is, the corrosion resistance of the roughened surface on the copper foil side when the copper foil well jj / from the Uze surface is softly etched with a mixture of sulfuric acid and 1 ^ hydrogenated hydrogen (The circuit corrosion resistance is effective.) From the above, the present invention provides: (4) for the υ-type printing f-path substrate, which is a layer containing the recording or the compound or the like on the subtraction surface of (4) (hereinafter referred to as "recording layer" </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> In the plating film of dm2 or more and 35 〇〇# g/dm or less, the ratio of nickel to gold in the plating film {nickel adhesion weight/(nickel weight 1 + zinc adhesion weight)} is 0.38 or more and 〇.7 or less. 2) The printing of the 荃 旦 & & quot 德 德 德 w w 4 4 4 4 4 4 4 4 w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w Below 0.55. 3) A copper foil for a printed circuit board, such as 1) or 2) - top # - &amp;# ^, 5, which is the chromate coating layer. The chrome adhesion weight of the early area of the anchorage is below 3〇#g/dm and less than 1〇〇#g/dm2.隹4) Copper foil for printed circuit boards contained in 3), as in 1) to 3), wherein the nickel-zinc layer contains ^ ^ ^ ^ ^ ^ The words of the form of cancer of oxide or zinc hydroxide account for 45 to 90%. Lizhong) The copper foil for printed circuit boards described in the item - the nickel-zinc layer contains the nickel oxide or nickel hydroxide in the nickel-zinc layer The brocade of the form is 6〇~8〇%. Milk 6) The copper foil for a printed circuit board as described in 1) to 5), which is further provided with a decane coupling agent layer on the chromate layer of 201002165. The copper foil for a printed circuit board according to any one of the above-mentioned, wherein the copper box is an electrolytic copper box, and the roughened surface is a rough surface during the electric recording, or the rough surface is advanced - The roughened surface or the roughened surface of the electrolytic copper foil is applied. (8) The copper box for a printed circuit board according to any one of the items 1 to 6, wherein the copper bromide is a rolled copper foil. The roughened surface is a surface on which the rolled copper foil is roughened. A copper-clad laminate for a printed circuit board is produced by laminating a copper-clad laminate for a printed circuit board and a resin substrate for a printed circuit board as described in any of the first to eighth embodiments. In the case of the copper case for a printed circuit board of the present invention, in order not to deteriorate the peel strength of the printed circuit board after the high temperature is maintained, the recording layer is used, and the use of the recording layer is not required. A heat-resistant layer made of brass. Thereby, the heat-resistant peel strength of the copper box can be greatly improved. Moreover, it is possible to obtain a copper box for circuit board which can effectively prevent the circuit defects caused by the medicine, and (4) a novel circuit board for improving the resistance to sulfuric acid and hydrogen peroxide (especially a semi-conductive seal #m 卞马印刷1... The copper-clad laminate for the yak conductor package substrate and the copper-clad laminate for bonding the steel, the tree and the substrate ((4) is a copper-clad laminate for semiconductor package substrates). #然m(四) A copper foil for printed circuit boards. [Embodiment] 8 201002165 Next, the present invention will be described in detail and in detail in order to facilitate the understanding of the present invention. The copper foil of the present invention can be used as both an electrolytic copper foil and a rolled steel foil, but in the case of electrolytic copper foil, it can be applied to a rough surface at the time of electroplating. Further, the rough surface may be further subjected to a roughening treatment. For example, in order to increase the peel strength of the resin substrate and the laminated copper box, an electrolytic copper foil which is subjected to a roughening treatment (for example, "tumor"-like electrodeposition of copper) is applied to the surface of the copper foil after degreasing, and Can be used directly. Generally, the side of the drum type electrolytic copper box manufacturing apparatus (the drum side) is a glossy surface, and the opposite side is a rough surface. In the case of a rolled copper foil, it is a calendered surface having a gloss on either side. In the present invention, although the electrolytic copper foil has a rough surface and a glossy surface, it can be used as it is when it is a rough surface. On the other hand, in order to further improve the peel strength, the glazed surface of the electrolytic copper foil is roughened to form a roughened surface. The rolled copper foil was similarly subjected to a roughening treatment. The roughening treatment, in any case, can be carried out using a known roughening treatment, and is not particularly limited. The roughened surface of the present invention refers to a rough surface during electroplating of an electrolytic copper foil, and a roughened surface of an electrolytic copper box or a rolled copper which is subjected to roughening treatment, and is applicable to all copper foils. First, the copper foil for the body package substrate is not provided with a brass coating layer which is considered to be necessary. In the past, if there is no brass coating layer, there is a concern that the characteristics of the copper box's separation strength (heat-resistant peel strength) may decrease after the printed circuit board is held at a high temperature for a certain period of time, but a nickel-zinc 9 201002165 layer is formed instead. Yellow steel is coated to enhance the peeling strength of the heat. Therefore, in this test, _/*, / was previously considered to be a common feature of the formation of a brass coating on the copper foil of common sense. The nickel-zinc layer, which is not a uniform nickel-zinc alloy, but contains one of nickel and zinc ... is an oxide or hydroxide I, for example, a nickel-containing layer containing a surface oxide film or barium hydroxide. The copper foil for a semiconductor package substrate of the present invention is a nickel-zinc layer formed on a roughened surface of a copper box (which is a surface of a resin), a chromate film layer, and, if necessary, a stone kiln. The mixture layer is composed of. For copper boxes, the above-mentioned calendering (4) or electrolytic copper can be used. Further, as the chromate coating layer, an electrolytic chromate coating layer or a chromate coating layer may be used. The above-mentioned 'for example, on the roughened surface of the copper foil, a layer containing bromine and zinc or these compounds (hereinafter referred to as "nickel layer") is formed, but it is necessary to make the copper of the above-mentioned zinc-recording layer. The attached weight per unit area is below 35 〇〇#g/dm on _g 乂. If the attached weight is less than 180# g/dm, the removal of the high temperature heating will be exacerbated. Further, if the zinc adhesion weight is 3500 # g/dm2 or more, the erosion of the end portion of the circuit caused by the sulfuric acid and the hydrogen peroxide system #etching liquid becomes remarkable. It is necessary to make {nickel adhesion weight / (nickel 荖 L, 骒 attached test + refill weight)} U.38 or more, 0 7 or less. If it does not reach 〇 a A · it will not effectively prevent circuit intrusion. Moreover, if it is 〇·7 or more, 4 thermal peeling strength will fall. The zinc layer is usually formed by the following conditions. However, as long as the word per unit area of the nickel layer is achievable, the weight is 180# g/dm2 or more and 3500 is less than g/dm2 (the nickel is attached more / (nickel adhesion weight + zinc adhesion 10 201002165 weight) When the plating conditions are 0.38 or more and 0.7 or less, there is no particular limitation. Other electric forging conditions may be used. (Mineral composition) Ni. l〇g/L~3 0g/L , Zn : lg / L ~ 15g / L, sulfuric acid (H2S04): lg / L ~ 12g / L for the basic plating bath. And if necessary, add chloride ions: lg / L ~ 5g / L. (current density) 3 ~40A/dm2 Next, the chromate coating is prepared, and the chromate treatment can be applied to electrolytic chromate treatment, impregnation chromate treatment, and zinc chromate treatment containing zinc in the chromate plating bath. In either case, if the chrome adhesion weight is less than 3 〇 # g/dm2, the effect of increasing acid resistance and heat resistance is small, so that the amount of chrome-attached weight is more than 30&quot;g/dm2. If the chromium adhesion weight exceeds 1 〇〇 # g/dm, the chromate treatment effect will be saturated, and the chromium adhesion weight can no longer be increased. If this is summarized, the chromate portion The chromium adhesion weight per unit area in the layer is preferably 3 〇 to 1 〇〇//g/dm 2 . Examples of the conditions for forming the above-described chromate coating layer are described below. However, as described above, it is not necessary to receive this. Limitation of conditions, well-known lysate treatment can be used. Generally, in the case of impregnation chromate treatment, the chromium adhesion reset per unit area can be achieved 30~40/zg/dm2. X, electrolytic chromate In the case of treatment, the chromium adhesion weight per unit area can be achieved by 3〇~i〇〇&quot;/dm2. This anti-money treatment is one of the factors affecting the acid resistance and heat resistance of the copper box. The chromate treatment is effective because it can improve the chemical resistance and fuel economy of the copper box. (a) A case of impregnation chromate treatment

Cr03 或 K2Cr207: 1〜12g/L，Zn(OH)2 或 ZnS04· 7H20 : 0〜10g/L，Na2S04 : 0〜20g/L，pH 2_5〜12.5，溫度：20〜 60°C，時間：0.5〜20秒 (b) 電解鉻酸鹽處理之一例Cr03 or K2Cr207: 1~12g/L, Zn(OH)2 or ZnS04·7H20: 0~10g/L, Na2S04: 0~20g/L, pH 2_5~12.5, temperature: 20~ 60°C, time: 0.5 ~20 seconds (b) An example of electrolytic chromate treatment

Cr03 或 K2Cr207 : 1 〜12g/L，Zn(OH)2 或 ZnS04· 7H20 : 0〜10g/L’Na2SO4:0〜20g/L，pH2.5〜12.5M：g^:20~ 6〇°C，電流密度0.5〜5A/dm2，時間：〇·5〜20秒 本發明之印刷電路基板用銅落所使用之矽烷偶合劑， 較佳為，至少含有四烷氧矽烷、與具備有具有與樹脂之反 應性之官能基的烷氧矽烷之i種以上。此矽烷偶合劑之選 擇亦為任意，但較佳為考慮與樹脂之接著性來加以選擇。 並且’本發明’提供—種上&amp; 1)〜8)之任-項所記載 之印刷電路基板用銅箱，及9)所記載之將印刷電路基板用 銅箱與樹脂基材加以貼合所製成之覆銅積層板。 # ;此防銹層上，施以矽烷偶合劑處理（塗布後， 矽炕偶合劑處理之條件如下述。Cr03 or K2Cr207 : 1 to 12g/L, Zn(OH)2 or ZnS04· 7H20 : 0~10g/L 'Na2SO4: 0~20g/L, pH2.5~12.5M: g^:20~ 6〇°C The current density is 0.5 to 5 A/dm 2 , and the time is 〇 5 to 20 seconds. The decane coupling agent used for the copper falling of the printed circuit board of the present invention preferably contains at least a tetraalkane, and a resin. One or more kinds of alkoxysilanes having a reactive functional group. The choice of the decane coupling agent is also arbitrary, but it is preferably selected in consideration of the adhesion to the resin. Further, the present invention provides a copper case for a printed circuit board according to any one of the items of the above-mentioned items, and a copper case for a printed circuit board and a resin substrate as described in 9). The copper clad laminate produced. #; This rustproof layer was treated with a decane coupling agent (after coating, the conditions of the oxime coupling treatment are as follows.

%之將m·2體積％之環氧石夕院（ep°xysi1叫與〇.4 I 缺 四6氣石夕燒）的水溶液調整成PH5，進行塗^ 然後加以乾燥。 退仃塗1 [試驗方法] 使用將上述太斗 式所製成之銅箱與下述之樹脂基材力, 12 201002165 積層接著而成的印刷電路基板，實施各試驗，進行銅箔與 樹月曰基材之欲合性的評價、與每單位面積之鎳及鋅的鑛敷 附著重量的測定。又，藉由XPS(X射線光電子光譜法）來測 定鎳鋅層中所含有之鎳及辞之價數為〇的金屬狀態與價數 為2的氧化狀態的存在比。 與銅箔積層之樹脂基材，係使用以下之2種類。 FR-4樹脂（玻璃布基材環氧樹脂） BT樹月曰（二氮雜苯_雙馬來亞醯胺系樹脂，商標名：三 菱瓦斯化學股份有限公司製GHPL-802) 另，BT樹脂，耐熱性高，係半導體封裝用印刷電路基 板所使用之材料。 (1)使用FR-4基板之常態剝離強度與耐熱剝離強度的 測定 對將銅箔形成有鎳辞層之面與FR_4樹脂基材加以積層 所製成的積層板上的銅箱進行蝕刻，在積層板上形成丨〇mm 寬的銅箔電路。將此電路加以剝離，測定常態剝離強度。 接著，測定將上述形成有l〇mm寬之銅箔電路的積層板於大 氣甲以180°C加熱2天後之剝離強度（以下稱為耐熱剝離強 度）、以及與該常態剝離強度相較之相對劣化率（損耗％)。 FR-4基板条與BT基板相比較，則耐熱性顯得較差。因此， 當使用FR-4基板時，若具有良好的耐熱剝離強度與低劣化 率，則使用BT基板時’亦會具有充分的耐熱剝離強度與劣 化率。 (2)使用BT基板之常態剝離強度與耐硫酸過氧化氫性 13 201002165 的測定 ’對將銅泊形成有鎳鋅層之面與BT樹脂基材加以積層所 製成的積層板上的銅炫、社^ 的銅·冶進行蝕刻，在積層板上形成 寬：銅v白電路。將此電路加以剝測定常態剝離強度。 接者使用上述形成有〇 4mm寬之銅箱電路的積層板，進 行耐硫酸、過氧化氫性試驗。 此4驗，係將積層板上之銅Ή路浸潰於含有硫酸1〇〇 〜4〇〇g/L、過氧化氫1()〜6()g/L的蚀刻液，將銅猪電路厚度 餘刻掉2 /z m德，、、目丨丨中_&amp;丨, 又 灸測疋剝離強度以及與該常態剝離強度相較 之相對劣化率（損耗％)。 ^ T之剝離強度的測定’可說是在過份嚴 下，當使用FR-4某杌拄你认 A 兄 伸击 基板時，係較一般所進行之耐藥品性的評 仏更加過份嚴酷的條件。因此，當使用BT基板時，若具有 良：：耐硫酸、過氧化氫性，則fr_4基板亦會具有充分的 财藥品性（特別是耐硫酸、過氧化氫性）。 ’ (3) 每單位面積之鎳及辞之鍍敷附著重量的測定 j㈣形成有録鋅層之面以露出於表面的方式與FR_4 樹脂基材積層，製作積芦板 於籍居把“ 以鹽酸或硝酸將露出 表面之_層與其母層之鋼加以㈣ 洛解液中之錄及鋅濃度的化學分 錄及鋅的附著重量。 來測疋母早位面積之 (4) 鋅及鎳之金屬/氧化狀態的解析 ^用xpsoc射線光電子光講法），來測定錄鋅層中所含 之、、及鋅之價數為。的金屬狀態與價數為2的氧化狀態 14 201002165 的存在比。、、則6 ’、疋，係一邊藉由氬離子濺鍍對銅箔厚度進 ♦虫刻，一邊；县太T&quot; 行， _ 表面至銅層（為鎳鋅層之基底）為止間歇地進 月 自最表面起之深度，將各深度所得之氧化狀態之鎳 人2的存在比加以積分，藉此計算出氧化鎳及氧化辞（皆包 S氫氧化物）在鎳辞層全體的平均存在比。 ^ 、疋斤使用之機器為KRATOS公司製造之AXIS-HS， 气離子濺鍍的輪出為525W。於此條件下，銅箔厚度會在1 分鐘被㈣掉約2‘濺鍍時間my⑽分鐘之條 行。 心 實施例 接著，說明實施例及比較例。其結果示於以下各表。 另本實施例僅為表示較佳之一例者，本發明並不限定於 此等之實施例。因此，包含於本發明之技術思想的變形、 其他之實施例或態樣，全部包含於本發明。 另，為了與本發明進行比對，係揭露有比較例。 (實施例1 - 7，比較例1 _ 2 ) 使用厚度12# m之電解銅箔，以下述所表示之條件， 藉由電鍍將鎳鋅層形成在此銅羯的粗化面（表面平均粗糙 度：3.8 a m)。每單位面積之鎳及鋅的鍍敷附著重量與鍍敷 被膜中的錄重量比率示於表1。 (電鍍液組成）Ni: 13g/L，Zn: 5g/L，硫酸（H2S04): 8.5g/L (電流密度）20A/dm2 (鍍敷時間）〇·5〜10秒 並且，在此鎳鋅層上，進行鉻酸鹽處理，形成防銹層。 15 201002165 以下表示處理條件。% of the aqueous solution of m. 2 vol% of Epoxy Stone Court (ep°xysi1 and 〇.4 I 缺四6石石夕烧) was adjusted to pH 5, coated and then dried.仃 仃 [ [ 试验 试验 试验 试验 试验 [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ The evaluation of the compatibility of the base material and the measurement of the adhesion weight of the mineral deposit per unit area of nickel and zinc. Further, XPS (X-ray photoelectron spectroscopy) was used to determine the ratio of the state of the metal contained in the nickel-zinc layer and the oxidized state in which the valence of nickel was 〇 and the valence number was 2. The following two types of resin substrates are laminated with a copper foil. FR-4 resin (glass cloth substrate epoxy resin) BT tree 曰 曰 (diaza benzene _ double malayan amide resin, trade name: Mitsubishi Gas Chemical Co., Ltd. GHPL-802) Another, BT resin It has high heat resistance and is a material used for a printed circuit board for semiconductor packaging. (1) Measurement of Normal Peel Strength and Heat Peeling Strength of FR-4 Substrate A copper box on a laminate formed by laminating a surface on which a nickel foil layer is formed with a FR-4 resin substrate is etched. A copper foil circuit having a width of 丨〇 mm is formed on the laminate. This circuit was peeled off and the normal peel strength was measured. Next, the peeling strength (hereinafter referred to as heat-resistant peeling strength) of the laminated sheet in which the copper foil circuit having the width of 100 mm was formed was heated at 180 ° C for 2 days, and the normal peel strength was measured. Relative deterioration rate (% loss). When the FR-4 substrate strip is compared with the BT substrate, the heat resistance appears to be poor. Therefore, when the FR-4 substrate is used, if it has a good heat-resistant peel strength and a low deterioration rate, the BT substrate will have sufficient heat-resistant peel strength and deterioration rate. (2) Normal peel strength and sulfuric acid-resistant hydrogen peroxide resistance using the BT substrate 13 Measurement of 201002165 'The copper plate on the laminate plate formed by laminating the surface of the nickel-zinc layer formed with copper and nickel on the BT resin substrate Etching of the company's copper and metallurgy, forming a wide: copper v white circuit on the laminate. This circuit was stripped to determine the normal peel strength. The laminate was subjected to the above-mentioned laminate having a copper box circuit having a thickness of 4 mm to carry out a sulfuric acid-resistant and hydrogen peroxide-resistant test. In the 4th test, the copper crucible on the laminated board is immersed in an etching solution containing sulfuric acid 1〇〇~4〇〇g/L, hydrogen peroxide 1()~6()g/L, and the copper pig circuit The thickness is 2 / zm, and the _&amp; 丨, and the moxibustion peel strength and the relative deterioration rate (loss %) compared with the normal peel strength. ^ The determination of the peel strength of T can be said to be too strict. When using FR-4, you recognize that A brother is striking the substrate, it is more harsh than the general evaluation of chemical resistance. conditions of. Therefore, when the BT substrate is used, if it has good: sulfuric acid resistance and hydrogen peroxide resistance, the fr_4 substrate also has sufficient chemical properties (especially sulfuric acid resistance and hydrogen peroxide resistance). ' (3) Measurement of the adhesion weight of nickel per unit area and the plating of j. (4) The surface of the zinc-coated layer is formed to be exposed on the surface and laminated with the FR_4 resin substrate to prepare a slab of slabs. Or nitric acid will be exposed to the surface layer of the steel layer and its parent layer (4) recorded in the Loose solution and the chemical concentration of zinc concentration and the adhesion weight of zinc. To measure the early area of the mother (4) zinc and nickel metal / analysis of the oxidation state ^ by xpsoc ray photoelectron method), the ratio of the metal state contained in the zinc-bearing layer and the valence of zinc to the existence ratio of the oxidation state 14 201002165 having a valence of 2 is determined. 6', 疋, while argon ion sputtering on the thickness of the copper foil into the worm, while the side; the county too T&quot; line, _ surface to the copper layer (the base of the nickel-zinc layer) intermittently into the moon From the depth of the outermost surface, the existence ratio of the nickel man 2 in the oxidation state obtained at each depth is integrated, thereby calculating the average existence ratio of the nickel oxide and the oxidized word (all of the S hydroxide) in the entire nickel layer ^, The machine used by 疋金 is AXIS- manufactured by KRATOS HS, the ion-sputtering round-out is 525 W. Under this condition, the copper foil thickness will be (4) off for about 2' sputtering time my (10) minutes in 1 minute. Heart Example Next, the examples and comparative examples are explained. The results are shown in the following tables. The present embodiment is merely a preferred embodiment, and the present invention is not limited to the embodiments. Therefore, modifications, other embodiments, or the like are included in the technical idea of the present invention. The invention is all included in the present invention. Further, in order to compare with the present invention, a comparative example is disclosed. (Examples 1 - 7, Comparative Example 1 - 2) Electrolytic copper foil having a thickness of 12 # m was used, with the following The conditions indicated are that a nickel-zinc layer is formed by electroplating on the roughened surface of the copper mat (surface average roughness: 3.8 am). The plating adhesion weight of nickel and zinc per unit area is recorded in the plating film. The weight ratio is shown in Table 1. (Plating solution composition) Ni: 13 g/L, Zn: 5 g/L, sulfuric acid (H2S04): 8.5 g/L (current density) 20 A/dm 2 (plating time) 〇·5~10 Secondly, on this nickel-zinc layer, chromate treatment is performed to form a rust-proof layer. 15 201002165 It shows the processing conditions.

Cr03 : 4.0g/L，ZnS04 · 7H20 : 2_0g/L，Na2S04 : 15g/L， pH : 4.2，溫度：45°C，電流密度3.0A/dm2，時間：1.5秒 16 201002165 财交例2 交例1 麵例7 勢包例6 雜例5 雜例4 細列3 麵例2 實施例1 Μ A/dm2 電流密度 Ni-Zn繼欠 2395 Η-* to 1981 1599 998 682 476 252 ►—» to 00 ^g/Hm2 Ni附著重量 鑛敷附著重量 - 3909 ►—* Ό 3381 , ί 2058 1292 ON 00 00 H—» 313 »—* //g/idm2 Zn附著重量 1 0.38 0.44 0.38 0.44 0.44 0.52 0.45 丨 0.45 0.40 Ni重量比率 1.67 1.51 丨 1.64 1.68 1—* 1.53 I—* L/i 1.57 1.57 kN/m 常態剝離 丨 FR-4細射生 I-—» ON 0.69 1.65 Lh Ol to 1.55 1—* L/&gt; 1.50 1.49 kN/m 而撫剝離 Ο 二 L/i Lh 二 相對劣化機 1.10 1.01 1.04 I ! 1.18 1.21 h—* o 1.04 1.24 1.20 kN/m 1_ 常態剝離 BT細射生 0.93 0.96 0.91 η-» S 1.07 0.93 0.93 1.09 1.08 1 kN/m 纖'過氧化1/懷理後 5； U) U) »—* c—* to 1—* 相對劣化糊 1_ 里- _ 201002165 由於電流密度固定（20A/dm2)，因此鍍敷附著重量係隨 著錄敷時間而變化。鍍敷時間係在〇 5〜丨〇秒之範圍來進行 處理。每單位面積之辞的附著重量為DA、”。# ， 鍍敷被膜中之鎳重量比率為37〜52重量％。此等之條件， 皆在本發明之範圍。 於FR-4基板之常態剝離強度為153〜i.68kN/m，耐熱 剝離強度為1.45〜1.65kN/m，劣化率在5%以下之範圍，皆 顯示出良好的常態剝離強度與耐熱剝離強度。另一方面， 於BT基板之常態剝離強度為丨〇4〜i.24kN/in之範圍。以 硫酸、過氧化氫混合液處理後的剝離強度為〇91〜 1.09kN/m ’劣化率為1〇〜13%，顯示出良好之性質。 然而，於比較例1中，辞之每單位面積的附著重量為 159 /z g/dm2 ’並不符合本發明。於此比較例1中，於 基板之常態剝離強度為1.51kN/m，耐熱剝離強度為 〇-69kN/m ’劣化率為54%，耐熱剝離強度大幅下降。 另一方面，於比較例2中，鋅的附著量為3909 # g/dm2， 並不符合本發明。於此比較例2中，於Βτ基板（過份嚴酶 之環境下）之常態剝離強度為1.10kN/m，以硫酸、過氧化氣 混合液處理後的剝離強度為〇.93kN/ni，劣化率為16%，具 有必要充分之特性。然而，由於Ni之附著重量變多，故在 形成銅箔電路時，Ni未受到蝕刻而殘留下來，成為電路不 良的原因。因此，作為印刷電路基板用銅箔之表面處理並 不適當’比較例2並不符合本發明。 由以上，於本實施例1〜7中，FR-4基板具有良好的剥 18 201002165 離強度與耐熱剝離強度，BT基板之耐硫酸、過氧化氨性試 驗顯示出良好的耐藥品性。因此，於本實施例中，高溫加 熱後之籾離強度的劣化少，且可理解保有可大幅改善電路 侵蝕現象之有效特性。 特別是在將樹脂基材與銅落加以積層，並使用硫酸、 過氧化氫系蝕刻液對電路進行軟蝕刻時，可得到能夠有效 防止電路侵蝕現象的銅箔表面處理技術。 (實施例8-13) 以下述所示之條件，改變電流密度，形成鎳辞層。每 單位面積之鎳及鋅的鍍敷附著重量、與鍍敷被膜中之鎳重 里比率不於表2 〇 (電流密度）3〜40 A/dm2 (鍵敷時間）0.5〜10秒 上述電流密度以外之製造條件，係與實施例1〜7相 同。基板之種類及剝離強度之測定亦為與實施例1〜7相同 的條件。此結果同樣地示於表2。 19 201002165 雜例13 WH12 實施例11 實施例10 雜例9 I 實施例8 NJ Η—* OJ A/dm2 電流密度 359 1--* 436 372 246 590 /zg/dm2 2 3 啉 rw 鑛敷附著重量 367丨 ! 588 _1 438 411 330 724 Γ /zg/dm2 Zn附著重量 1_ 0.49 0.52 _1 0.50 0.48 0.43 0.45 Ni重量比率 1—» 1—- 1.48 1.48 1.50 1.56 1.50 m/m i_ 常態剝離 FR4細射生 1.47 1.50 1.40 Ι-— U\ 1—- K) kN/m 而ί熱剝離 to 二 〇\ to 相對劣化機 0.98 1.04 _1 1—— S s 0.98 0.92 kN/m 常態剝離 BT基板榭生 0.96 1 1 1 0.93 _1 0.98 i 0.94 0.91 0.88 kN/m 獄' 過氧化遽理後 U) 1—* 00 00 相對劣化綱 201002165 旦鑛敷附著重量如表2所示，每單位面積之辞的附著重 篁為330〜724#g/dm2,鍍敷被膜中之鎳重量比率為43〜52 重里％。此等之條件，皆在本發明之範圍。 若電流密度低於3A/dm2,則由於不會生成錄辞層故 作為本案之錦鋅層的鑛敷條件並不適當。X，若電流密产 超過4〇A/dm2，則由於在陰極（銅箱）會產生大量的氯^電= 效率會變得極低，故作為鎳鋅層的處理條件並不適當。因L 此，形成本案之鎳鋅層時的電流密度，較佳為3〜仙 於FR-4基板之常態剝離強度為i 48叫祕⑽，耐献 剝離強度為U045細m，劣化率在7%以下的範圍，皆 顯示出良好的常態剝離強度與耐熱剥離強度。 另-方面，於BT基板之常態剝離強度為〇·92〜 1.04kN/in，以疏酸、過氣介急、、θ人 ，故力氣化氫此合液處理後的剝離強度為 〇別〜〇.98kN/m，劣化率為3〜11%，顯示出良好的性質。 由以上’於本實施例8〜13中，F“基板具有良好的Cr03 : 4.0g / L, ZnS04 · 7H20 : 2_0g / L, Na2S04 : 15g / L, pH : 4.2, temperature: 45 ° C, current density 3.0A / dm2, time: 1.5 seconds 16 201002165 Financial Interchange 2 1 Surface example 7 Potential package example 6 Miscellaneous 5 Hybrid 4 Detail 3 Surface example 2 Example 1 Μ A/dm2 Current density Ni-Zn continuation 2395 Η-* to 1981 1599 998 682 476 252 ►—» to 00 ^g/Hm2 Ni adhesion weight mineral deposit weight - 3909 ►—* Ό 3381 , ί 2058 1292 ON 00 00 H—» 313 »—* //g/idm2 Zn adhesion weight 1 0.38 0.44 0.38 0.44 0.44 0.52 0.45 丨0.45 0.40 Ni weight ratio 1.67 1.51 丨1.64 1.68 1—* 1.53 I—* L/i 1.57 1.57 kN/m Normal peeling 丨FR-4 fine shot I-—» ON 0.69 1.65 Lh Ol to 1.55 1—* L/&gt 1.50 1.49 kN/m and peeling Ο two L/i Lh two relative deterioration machine 1.10 1.01 1.04 I ! 1.18 1.21 h—* o 1.04 1.24 1.20 kN/m 1_ Normal stripping BT fine shot 0.93 0.96 0.91 η-» S 1.07 0.93 0.93 1.09 1.08 1 kN/m Fiber 'Peroxidation 1 / 5 after treatment; U) U) »—* c—* to 1—* Relative deterioration paste 1_ 里 - _ 201002165 Due to fixed current density (20A/dm2 Therefore, the plating adhesion weight varies depending on the recording time. The plating time is processed in the range of 〇 5 to leap seconds. The adhesion weight per unit area is DA, ".#, and the weight ratio of nickel in the plating film is 37 to 52% by weight. These conditions are within the scope of the present invention. Normal peeling of the FR-4 substrate The strength is 153 to i.68 kN/m, the heat-resistant peel strength is 1.45 to 1.65 kN/m, and the deterioration rate is in the range of 5% or less, and both exhibit good normal peel strength and heat-resistant peel strength. On the other hand, the BT substrate is used. The normal peel strength is in the range of 丨〇4 to i.24 kN/in. The peel strength after treatment with a mixture of sulfuric acid and hydrogen peroxide is 〇91 to 1.09 kN/m, and the deterioration rate is 1 〇 to 13%, which shows Good properties. However, in Comparative Example 1, the adhesion weight per unit area was 159 /zg/dm2'. This is not in accordance with the present invention. In Comparative Example 1, the normal peel strength on the substrate was 1.51 kN/ m, the heat-resistant peel strength was 〇-69 kN/m, the deterioration rate was 54%, and the heat-resistant peel strength was greatly lowered. On the other hand, in Comparative Example 2, the adhesion amount of zinc was 3,909 # g/dm 2 , which did not conform to the present invention. In Comparative Example 2, the normal peeling of the Βτ substrate (in the environment of excessively strict enzyme) The strength is 1.10 kN/m, and the peel strength after treatment with a mixture of sulfuric acid and peroxygen gas is 〇.93 kN/ni, and the deterioration rate is 16%, which has sufficient characteristics. However, since the adhesion weight of Ni is increased, When a copper foil circuit is formed, Ni is not etched and remains, which causes a circuit failure. Therefore, the surface treatment of the copper foil for a printed circuit board is not appropriate. [Comparative Example 2 does not conform to the present invention. In the first to seventh embodiments, the FR-4 substrate has good peel strength and heat-resistant peel strength, and the sulfuric acid-resistant and ammonia peroxide test of the BT substrate showed good chemical resistance. Therefore, in the present embodiment, In the middle, the deterioration of the enthalpy strength after the high-temperature heating is small, and it is understood that the effective property of greatly improving the circuit erosion phenomenon is maintained. In particular, the resin substrate and the copper drop are laminated, and sulfuric acid or hydrogen peroxide-based etching liquid is used. When the circuit is soft-etched, a copper foil surface treatment technique capable of effectively preventing circuit erosion can be obtained. (Example 8-13) The current density is changed under the conditions shown below to form Nickel layer, the plating adhesion weight of nickel and zinc per unit area, and the nickel weight ratio in the plating film are not shown in Table 2 电流 (current density) 3~40 A/dm2 (bonding time) 0.5~10 seconds The production conditions other than the above current densities were the same as those of Examples 1 to 7. The measurement of the type of the substrate and the peeling strength were also the same as those of Examples 1 to 7. The results are similarly shown in Table 2. 19 201002165 13 WH12 Example 11 Example 10 Example 9 I Example 8 NJ Η—* OJ A/dm2 Current density 359 1--* 436 372 246 590 /zg/dm2 2 3 porphyrin rw Mineral deposit weight 367丨! 588 _1 438 411 330 724 Γ /zg/dm2 Zn adhesion weight 1_ 0.49 0.52 _1 0.50 0.48 0.43 0.45 Ni weight ratio 1—» 1—- 1.48 1.48 1.50 1.56 1.50 m/m i_ Normal stripping FR4 fine shot 1.47 1.50 1.40 Ι- — U\ 1—- K) kN/m and 剥离 heat stripping to 〇 \ to relative deterioration machine 0.98 1.04 _1 1 — S s 0.98 0.92 kN/m Normal stripping BT substrate twin 0.96 1 1 1 0.93 _1 0.98 i 0.94 0.91 0.88 kN/m Prison 'Urea after oxidation O) 1—* 00 00 Relative Deterioration 201002165 As shown in Table 2 with the weight, per unit area of the speech emphasis is attached to Huang 330~724 # g / dm2, the nickel weight ratio in the plating film is in 43~52 weight%. These conditions are within the scope of the invention. If the current density is less than 3 A/dm2, since the recording layer is not formed, the mineralization conditions of the zinc-coated layer of the present invention are not appropriate. X. If the current density is more than 4 〇A/dm2, a large amount of chlorine is generated in the cathode (copper box) = the efficiency is extremely low, so the processing conditions for the nickel-zinc layer are not appropriate. Because of L, the current density when forming the nickel-zinc layer of the present invention is preferably from 3 to 10, and the normal peel strength of the FR-4 substrate is i 48 (10), and the peel strength is U045 fine m, and the deterioration rate is 7 The range below % shows good normal peel strength and heat peel strength. On the other hand, the normal peel strength of the BT substrate is 〇·92~1.04kN/in, and the peeling strength after the liquid treatment is the same as the acidity, the gas, and the θ person. 〇98 kN/m, the deterioration rate was 3 to 11%, showing good properties. From the above, in the eighth to thirteenth embodiments, the F" substrate has a good

剝離強度與耐熱剝離強度，BT美拓目,丨, A I扳則顯不出良好的耐硫 酸、過氧化氫性。因此，於太瞢姑A，丄 於本貫施例中，高溫加熱後之剝 離強度的劣化少，可理解保有可夬 令』大‘改善電路侵蝕現象之 有效特性。 (實施例1、7、14，比較例3、4) 接著’說明鍍敷被膜中之Ni舌旦 〈Nl重里比率的範圍。作為一 例，實施例1、7、14及比較例卩、4 + 权例3、4不於表3。又，每單位 面積之鎳及鋅的鍍敷附著重量耝 $興鑛敷破膜中的鎳重量比率 示於表3。 21 201002165 上述以外之製造條件，係與實施例卜13相同。基板 之種類及剝離強度之測定亦為與實施例！〜Η相同的條 件。此結果同樣地示於表3。鍍敷被膜中的川重量比率為 〇. 3 8 〜〇 · 5 4。 於FR-4基板之常態剝離強度為I.54〜l.64kN/m， 剝離強度為1_42〜1.65kN/m,劣化率在8%以下的範0 顯示出良好的常態剝離強度與耐熱剝離強度。 22 201002165 BT基板榭生 獄、過氧化里後 ... 1相對劣化率(％) 1 m Ο 〇\ ldSf/m 0.91 1.08 0.91 0.91 0.92 常態剝離 kN/m 1.04 1.20 1,07 i ———1 &lt;N T—M 1.01 FR4細射生 而撒剝離 I 1相對劣化率(％) 1 ϊ—-( in 00 〇 cn (N | kN/m 1 l〇 1.49 1.42 0.97 i 1.02 常態剝離 1 1 kN/m 1 1.64 r- to 1—H 1.54 _ — _l ON CO 1.50 鑛敷附著重量 Ni重量比率 i- 0.38 | 0.40 0.54 0.37 i 0.76 ! Zn附著重量 L ... //g/dm2 3381 I11 H 619 206 233 ! Ni附著重量 1_ yg/dm2 1981 oo (N r1 tn CN 745 I i電流密度 1_ A/dm2 CN o 實施例7 tnm l 倾例14 tb|交例3 tbfe例 4 201002165 另方面⑤BT基板之常態_離&amp; &amp; ^ ^ ~ 1.20kN/m，以硫酸、過氧化氫混合液處理後的剝離強度為 O.^HN/m，劣化率為n〜15%’顯示出良好的性質。 然而，於比較例3 +，Ni重量比率》Q 37，並不符合 本發明。於此比較例3中，於FR_4基板之常態剝離強度為 1.39kN/m’ 4熱剝離強度為〇.97kN/m，劣化率為3〇%，财 熱剝離強度大幅下降。 另一方面，於比較例4中，Ni重量比率為〇 76，並不 符合本發明。於此比較例4中，於FR_4基板之常態剝離強 度為1.50kN/m，耐熱剝離強度為1〇2kN/m，劣化率為32 %，與比較例3同樣地，耐熱剝離強度大幅下降。 因此，鍍敷被膜中的Ni重量比率的範圍，較佳為〇 38 〜0.70，更佳為0.40〜0.54。 (實施例15〜19) 以下述所示之條件，改變鍍敷浴組成，形成鎳鋅層。 每單位面積之鎳及鋅的錢敷附著重量與鍍敷被膜中的鎳重 量比率示於表4。在此，與實施例1〜14不同之處在於改變 鑛敷浴之成分組成。 實施例15〜1 9之鍍敷浴的成分組成表示如下。 (實施例15之鍍敷液組成）Ni : 10g/L，Zn : lg/L，硫酸 (H2S04) : 8.5g/L。 (實施例16之鍍敷液組成）Ni : 20g/L，Zn : 8g/L，硫酸 (H2S04) : lg/L。 (實施例17之鍍敷液組成）Ni : 25g/L，Zn : 12g/L，硫 24 201002165 酸（H2S〇4) : 12g/L。 (實施例18之鍍敷液組成）Ni : 30g/L，Zn : 15g/L，硫 酸（H2S04) : 8.5g/L。 (實施例19之鍍敷液組成）Ni : 10g/L，Zn : lg/L，硫酸 (H2S04) : 6g/L，氯化物離子：5g/L。 (電流密度）2〇〜25A/dm2 (鍍敷時間）1〜8秒 上述以外之製造條件，係與實施例1〜7相同。基板之 ( 種類及剝離強度之測定亦為與實施例1〜7相同的條件。此 結果同樣地示於表4。Peel strength and heat-resistant peel strength, BT beauty extension, 丨, A I pull can not show good resistance to sulfuric acid, hydrogen peroxide. Therefore, in Taishanggu A, in the present example, the deterioration of the peel strength after high-temperature heating is small, and it is understood that there is an effective feature of improving the circuit erosion phenomenon. (Examples 1, 7, and 14, Comparative Examples 3 and 4) Next, the range of the ratio of the Ni tongue to the Nl ratio in the plating film will be described. As an example, Examples 1, 7, and 14 and Comparative Examples 4 and 4 + 权 3 and 4 are not shown in Table 3. Further, the plating adhesion weight per unit area of nickel and zinc 耝 $ the weight ratio of nickel in the blasting film is shown in Table 3. 21 201002165 The manufacturing conditions other than the above are the same as those in the embodiment. The type of substrate and the measurement of peel strength are also the same as in the examples! ~ Η the same conditions. This result is also shown in Table 3. The weight ratio of the Sichuan in the plating film is 〇. 3 8 〇 〇 · 5 4 . The normal peel strength of the FR-4 substrate is 1.54 to 1.64 kN/m, the peel strength is 1 to 42 to 1.65 kN/m, and the deterioration rate of 8% or less shows good normal peel strength and heat-resistant peel strength. . 22 201002165 BT substrate after jail, after peroxide... 1 Relative deterioration rate (%) 1 m Ο 〇\ ldSf/m 0.91 1.08 0.91 0.91 0.92 Normal stripping kN/m 1.04 1.20 1,07 i ———1 &lt;NT-M 1.01 FR4 fine shot and peeling I 1 relative deterioration rate (%) 1 ϊ—-(in 00 〇cn (N | kN/m 1 l〇1.49 1.42 0.97 i 1.02 Normal stripping 1 1 kN/ m 1 1.64 r- to 1—H 1.54 _ — _l ON CO 1.50 Mineral deposit adhesion weight Ni weight ratio i- 0.38 | 0.40 0.54 0.37 i 0.76 ! Zn adhesion weight L ... //g/dm2 3381 I11 H 619 206 233 ! Ni adhesion weight 1_ yg / dm2 1981 oo (N r1 tn CN 745 I i current density 1_ A / dm2 CN o Example 7 tnm l pour case 14 tb | example 3 tbfe example 4 201002165 another aspect 5BT substrate normal _Off &amp;&amp; ^ ^ ~ 1.20kN/m, the peel strength after treatment with a mixture of sulfuric acid and hydrogen peroxide is O.^HN/m, and the degradation rate is n~15%', showing good properties. In Comparative Example 3 +, Ni weight ratio "Q 37" does not conform to the present invention. In Comparative Example 3, the normal peel strength on the FR_4 substrate was 1.39 kN/m' 4 The thermal peel strength was 〇.97 kN/m. The deterioration rate was 3%, and the thermal peeling strength was greatly lowered. On the other hand, in Comparative Example 4, the Ni weight ratio was 〇76, which did not conform to the present invention. In Comparative Example 4, the normal peeling of the FR_4 substrate was performed. The strength was 1.50 kN/m, the heat-resistant peel strength was 1〇2 kN/m, and the deterioration rate was 32%. As in Comparative Example 3, the heat-resistant peel strength was largely lowered. Therefore, the range of the weight ratio of Ni in the plating film was higher. Preferably, it is 38 to 0.70, more preferably 0.40 to 0.54. (Examples 15 to 19) The composition of the plating bath is changed to form a nickel-zinc layer under the conditions shown below. The adhesion of nickel and zinc per unit area is adhered. The weight ratio of the weight to the nickel in the plating film is shown in Table 4. Here, the difference from Examples 1 to 14 is that the composition of the mineral bath is changed. The composition of the plating bath of Examples 15 to 19 is shown. The composition of the plating solution of Example 15 was Ni: 10 g/L, Zn: lg/L, and sulfuric acid (H2S04): 8.5 g/L. (The composition of the plating solution of Example 16) Ni: 20 g/L, Zn: 8 g/L, sulfuric acid (H2S04): lg/L. (Composition of plating solution of Example 17) Ni: 25 g/L, Zn: 12 g/L, sulfur 24 201002165 Acid (H2S〇4): 12 g/L. (The composition of the plating solution of Example 18) Ni: 30 g/L, Zn: 15 g/L, sulfuric acid (H2S04): 8.5 g/L. (The composition of the plating solution of Example 19) Ni: 10 g/L, Zn: lg/L, sulfuric acid (H2S04): 6 g/L, chloride ion: 5 g/L. (Current density) 2 〇 to 25 A/dm 2 (plating time) 1 to 8 seconds The production conditions other than the above were the same as in Examples 1 to 7. The measurement of the type and peel strength of the substrate was also the same as in Examples 1 to 7. The results are shown in Table 4 in the same manner.

25 201002165 BT細射生 猶、過氧化氫水處理後 相對劣化糊 i_ 卜 Os 00 00 kN/m 0.91 0.89 0.91 0.97 0.96 常態剝離 kN/m 1.09 0.98 0.98 1.09 1.04 Π1·4細射生 对熱剝離 相對劣化糊 CN (N (N 卜 kN/m 〇\ —— 1.56 卜 in 1.47 常態剝離 kN/m 1.57 CN (N in 1.59 00 in 緻谢著重量 Μ重量比率 0.50 0.45 0.45 0.44 0.48 Zh附著重量 yg/dm2 1 320 817 807 467 Ni附著重量 ^g/dm2 318 r N 00 m 668 卜 m \〇 425 Ni-Zn 織 電流密度 A/dm2 (N 實施例15 實施例16 實施例17 實施例18 實施例19 201002165 、每單位面積之鋅的附著重量為32〇〜817Wdm2，鍍 敷被膜中之鎳重里比率為44〜5〇重量％。此等之條件，皆 . 在本發明之範圍。 於FR_4基板之常態剝離強度為1.52〜1.62kN/m，财熱 剝離強度為1.47〜1.5_„1，劣化率為7%以下之範圍，皆 顯示出良好的剝離強度與耐熱剝離強度。 方面於B T基板之常態剝離強度為〇, 9 8〜 f U9kN/m °以硫酸、過氧化氫混合液處理後的剝離強度為 〇-97kN/m,劣化率為8〜17%，顯示出良好之性質。 由以上，於本實施例15〜19中，FR_4基板具有良好的 • 離強度與耐熱剝離強度’ BT基板則顯示出良好的耐硫酸 過氧化氫性。因此’於本實施例中，高溫加熱後之剝離強 度的劣化J，可理解保有可大幅改善電路侵蝕現象之有效 特性。 由以上，在製作本發明之鎳鋅層時的鍍敷浴的條件， ί.=佳為鎳濃度10〜3〇g/L’鋅濃度1〜15g/L，硫酸濃度卜 = g/L，氯化物離子〇〜5g/L。若不在此等之濃度範圍，鎳 或辞7辰度變濃’則由於會對廢水處理造成影響，因此作為 鍍敷/合之條件並不佳。又，若成分濃度偏低時，則除了會 敷之農度變化等的主要原因造成鍍敷浴的管理困難以 包流效率會極度降低’因此作為鍍敷浴之條件並 不佳。 (實施例20〜22) 在此’說明改變鉻酸鹽處理之方法時的實施例。 27 201002165 本實施例’係以與實施例&quot;相同所示的條件，來形成 錄鋅層° 4 了進行比較，電流密度與鍍敷時間係為相同的 條件（電流密度20A/dm2,鍍敷時間i 8秒）。每單位面積之 鎳及辞的鍍敷附著重量與鍍敷被膜中之鎳及鋅的重量比 率’同樣地示於表5。 在此，與實施例1〜7不同之處，在於改變鉻酸鹽處理 之條件。於實施例丨〜7中，進行有電解鋅鉻酸鹽處理。實 施例2 0〜2 2之鉻酸鹽處理的條件如下述。 (實施例20之鉻酸鹽處理）此係在鉻酸鹽浴中不含有鋅 之電解鉻酸鹽處理。25 201002165 BT fine shot raw, hydrogen peroxide water treatment after the relative deterioration paste i_ Bu Os 00 00 kN / m 0.91 0.89 0.91 0.97 0.96 Normal stripping kN / m 1.09 0.98 0.98 1.09 1.04 Π 1 · 4 fine shot on the thermal peeling relative Degraded paste CN (N (N b kN / m 〇 \ - 1.56 卜 in 1.47 normal stripping kN / m 1.57 CN (N in 1.59 00 in thanks to weight Μ weight ratio 0.50 0.45 0.45 0.44 0.48 Zh adhesion weight yg / dm2 1 320 817 807 467 Ni adhesion weight ^g / dm2 318 r N 00 m 668 卜 m \ 425 Ni-Zn woven current density A / dm2 (N Example 15 Example 16 Example 17 Example 18 Example 19 201002165 The adhesion weight per unit area of zinc is 32 〇 to 817 Wdm 2 , and the nickel weight ratio in the plating film is 44 to 5 〇 wt%. These conditions are all within the scope of the present invention. Normal detachment of the FR_4 substrate The strength is 1.52~1.62kN/m, the thermal peeling strength is 1.47~1.5_„1, and the degradation rate is 7% or less, which shows good peel strength and heat-resistant peel strength. Aspects of normal peel strength of BT substrate For 〇, 9 8~ f U9kN/m ° with sulfuric acid, The peel strength after the treatment with the hydrogen peroxide mixed solution was 〇-97 kN/m, and the deterioration rate was 8 to 17%, showing good properties. From the above, in the present Examples 15 to 19, the FR_4 substrate had good strength. The BT substrate exhibits good resistance to sulfuric acid hydrogen peroxide with the heat-resistant peel strength. Therefore, in the present embodiment, the deterioration J of the peel strength after high-temperature heating can be understood to have an effective characteristic that can greatly improve the circuit erosion phenomenon. From the above, the conditions of the plating bath in the production of the nickel-zinc layer of the present invention, ί.= preferably nickel concentration 10~3〇g/L' zinc concentration 1~15g/L, sulfuric acid concentration bu=g/L, Chloride ion 〇~5g/L. If it is not in these concentration ranges, nickel or yue 7 becomes thicker, it will affect the wastewater treatment, so the conditions for plating/combination are not good. When the concentration of the component is low, the management of the plating bath is difficult, and the flow efficiency is extremely lowered, in addition to the change in the degree of agronomic change. Therefore, the conditions for the plating bath are not good. (Examples 20 to 22) Here's the implementation of the method of changing the chromate treatment 27 201002165 This embodiment is based on the same conditions as the embodiment, to form a zinc coating layer. 4 The current density and the plating time are the same (current density 20A/dm2, Plating time i 8 seconds). The plating adhesion weight per unit area of nickel and rhodium is shown in Table 5 in the same manner as the weight ratio of nickel to zinc in the plating film. Here, the difference from Examples 1 to 7 is that the conditions of the chromate treatment are changed. In Examples 丨 to 7, an electrolytic zinc chromate treatment was carried out. The conditions of the chromate treatment of Example 2 0 to 2 2 are as follows. (Chromate treatment of Example 20) This was an electrolytic chromate treatment which did not contain zinc in the chromate bath.

Cr03: 6.0g/L ’pH: 10_0 ’溫度：25°C，電流密度：2A/dm2， 時間：2秒。 (實施例2 1之絡酸鹽處理）此係電解鋅鉻酸鹽處理。 Cr03 : 1.5g/L，ZnS04 · 7H2〇 : l_0g/L，Na2S04 : 10g/L， PH : 4.5 ’溫度：50°C ’電流密度：1.5A/dm2，時間：2秒。 (實施例22之鉻酸鹽處理）此係浸潰鋅鉻酸鹽處理。 Cr03 : 3.5g/L，ZnS04 · 7H2〇 : 2_4g/L，Na2S〇4 : 15g/L， PH : 4.2，溫度：40°C，時間：i〇 秒。 基板之種類及剝離強度之測定為與實施例1〜7相同的 條件。此結果同樣地示於表5。 28 201002165 BT細射生 I j 石誠'過氧化理後 相對劣化糊 00 卜 版/m 0.94 0.83 1- 0.98 1 常態剝離 kN/m 1.03 1.01 1.08 脳細射生 而撫剝離 相對劣化糊 m cn cn kN/m 1.47 1 1.50 rn 常態剝離 kN/m 1.51 1 1.54 1.48 鍍敷附著重量 ΝΪ重量比率 0.43 0.46 0.47 Zn附著重量 ^g/dm2 434 552 347 Ni附著重量 β%/άπχ 329 r_·〆 312 Ni-Zn 織 電流密度 _1 A/dm2 實施例20 實施例21 實施例22 201002165 如f所示，實施例20〜22,鋅之附著量為347〜552 比率為43〜47重量％。此等之條件皆在本發 明之範圍。於FR-4基板之常態剝離強度為“8〜 iWkN/m’耐熱剝離強度$ 143〜15QkN/m，劣 %以下之範圍’皆顯示出良好的剝離強度。 μ . '、、 另-方面’於ΒΤ基板之常態剝離強度為ι 〇ι〜 USkN/m’以硫酸、過氧化氫混合液處理後的 一細一劣化率為8〜17% ’顯示出良好的性；為 由以上，於本實施例20〜U中，FR_4基板具 剝離強度與耐埶性，B τ芙# &amp; 义 的 卜 性BT基板顯不出良好的耐硫酸、過氧化 虱性。因此，於本實施例，高溫加熱後之剝離強度的劣化 少^理解藉由選擇基板與敍刻液，可保有可大幅改善電 路侵蝕現象之有效特性。 從實施例20〜22可知，本案之形成有錄辞層之銅落的 耐熱性與耐藥品性’由於會 ^鉻酸鹽處理之種類的影 響因此可適用各種鉻酸鹽處理作為防錢處理。 從以上之實施例及比較例可知，本發明幾乎不會發生Cr03: 6.0 g/L ‘pH: 10_0 ′ Temperature: 25° C., current density: 2 A/dm 2 , time: 2 seconds. (Example 2 lysate treatment) This is an electrolytic zinc chromate treatment. Cr03 : 1.5 g / L, ZnS04 · 7H2 〇 : l_0g / L, Na2S04 : 10g / L, PH : 4.5 ' Temperature: 50 ° C ' Current density: 1.5 A / dm 2 , time: 2 seconds. (Chromate treatment of Example 22) This was impregnated with zinc chromate treatment. Cr03 : 3.5 g / L, ZnS04 · 7H2 〇 : 2_4 g / L, Na 2 S 〇 4 : 15 g / L, pH : 4.2, temperature: 40 ° C, time: i 〇 seconds. The types of the substrates and the peel strength were measured under the same conditions as in Examples 1 to 7. This result is also shown in Table 5. 28 201002165 BT Fine Shot Student I j Shi Cheng 'Peroxidation After Relative Deterioration Paste 00 Bu Edition/m 0.94 0.83 1- 0.98 1 Normal Peeling kN/m 1.03 1.01 1.08 脳 Fine shot and peeling relative deterioration paste m cn cn kN/m 1.47 1 1.50 rn Normal peeling kN/m 1.51 1 1.54 1.48 Plating adhesion weight ΝΪ weight ratio 0.43 0.46 0.47 Zn adhesion weight ^g/dm2 434 552 347 Ni adhesion weight β%/άπχ 329 r_·〆312 Ni- Zn weave current density _1 A/dm 2 Example 20 Example 21 Example 22 201002165 As shown in f, Examples 20 to 22, the adhesion amount of zinc was 347 to 552, and the ratio was 43 to 47% by weight. These conditions are within the scope of the invention. The normal peel strength of the FR-4 substrate is "8~ iWkN/m' heat-resistant peel strength $ 143 to 15 QkN/m, and the range below the % is good". The good peel strength is shown. μ. ',, and other aspects' The normal peeling strength of the substrate is ι 〇ι~ USkN/m', and the fineness degradation rate after treatment with sulfuric acid or hydrogen peroxide mixture is 8 to 17%', showing goodness; In Examples 20 to U, the FR_4 substrate had peel strength and tamper resistance, and the B τ Fu # amp 的 BT substrate showed no good resistance to sulfuric acid and bismuth peroxide. Therefore, in the present embodiment, the temperature was high. The deterioration of the peeling strength after heating is small. It is understood that by selecting the substrate and the engraving liquid, the effective characteristics of the circuit erosion phenomenon can be greatly improved. From Examples 20 to 22, the formation of the copper layer of the recording layer is known. Since heat resistance and chemical resistance are affected by the type of chromate treatment, various chromate treatments can be applied as the anti-money treatment. From the above examples and comparative examples, the present invention hardly occurs.

Si二氧化氫液所造成之粗化面的侵敍，·高溫加熱後 度的劣化少等，在不會降低以往之由黄銅所構成 4理層的特性下’可大幅改善電路侵蝕現象。 接者，說明本案之錄鋅層所含之錄及辞的化學狀態。 :-般合金鍍敷被膜’構成被膜之金屬元素為合金 存在於最表層之極小部分的金屬元素因與大氣 而呈虱化狀態。 30 201002165 辞入之測定結果，本案之錄辞層並非鲜 鋅:金本身，被膜中之錄及鋅具有〇價之金屬狀態與2價 化狀態（氧化物或氫氧化物）不僅共存於最表層且還* 子於銅之基底的構造。例如於實施例14中，被膜中之全邙 鎳中’為氧化物或氫氧化物之化學形態者佔 之全部鋅中，呈2價之氧化狀態者姑㈣。 皮膜中 本案之藉由表面處理所得之錄辞層，被膜中之全 中，可確認為氧化物或氫氧化物之化學形態者的比率範圍 為45〜90%，同樣地被臈中之全部錦中，為氧化物或氯氧 化物之化學形態者的比率範圍為6〇〜80%。如實施例所 不，可確認於此種構成下，可欲松&amp; ^ 战下可發揮所欲之特性與效果。本 發明’係包含此專之條件全部者。 於上述中雖對適用於電解銅箱之粗化面之情形進行 說明，但是當然地亦同樣適用於光澤面經施以粗化處理之 電解銅羯。並且經施以粗化處理之壓延銅落亦相同。若使 用電解mi及壓延銅箱之粗化面’雖然會因粗化處理之形 狀、表面粗链度的不同，使得常態剝離強度之絕對值產生 不同’但是可降低耐熱剝離強度及硫酸、過氧化氫水處理 後之剝離強度與常態剥離相較的相對劣化率。 於本發明之印刷電路某柘用钿吱 ..„ 丞板用銅治，特別是將選擇鎳鋅 層之最佳條件作為發明之中心課題。藉此，以大幅提升鋼 落之对熱剝離強度’且有效防止電路侵姓現象，使耐硫酸、 過氧化氫性恒常穩定地發揮效力。 因此應可谷易理解電解銅箱及壓延銅箱之選擇或粗 31 201002165 化面之選擇，可視目的來任意地加以選擇。 産業上之可利用性 如以上所示’本發明之印刷電路基板用銅箔為了不 使间溫加熱後與樹脂之剝離強度劣化，故係使用鎳鋅層， 而可大幅提升銅箔之耐熱剝離強度。又，藉此能夠賦予可 =效防止電路侵蝕現象，可使耐硫酸、過氧化氫性忮常穩 疋地务揮效力之新穎特性，近年來印刷電路之微細圖案化 =頻化發展中’可適用作為印刷電路基板用鋼&amp;特別是 體封裝基板用銅箔)及將鋼箔與樹脂基材加以貼合所製 、之印刷電路基板（特別是半導體封裝基板）用覆銅積層板。 【圖式簡單說明】 無 【主要元件符號說明】 無 32The intrusion of the roughened surface caused by the Si hydrogen dioxide liquid, and the deterioration of the degree after the high-temperature heating are small, and the circuit erosion phenomenon can be greatly improved without lowering the characteristics of the conventional four-layered layer made of brass. Receiver, indicating the chemical status of the recorded and contained words in the zinc layer recorded in this case. : General alloy plating film 'The metal element constituting the film is an alloy. The metal element present in a very small part of the outermost layer is deuterated with the atmosphere. 30 201002165 The results of the resignation test, the record layer of this case is not fresh zinc: gold itself, the film recorded in the film and the metal state of zinc and the divalent state (oxide or hydroxide) not only coexist in the outermost layer And also * the structure of the base of copper. For example, in Example 14, in all of the zinc in which the chemical form of the total ruthenium nickel in the film is oxide or hydroxide, it is a divalent oxidation state (4). In the film, the recording layer obtained by the surface treatment in the present case, the ratio of the chemical form of the oxide or hydroxide in the entire film is 45 to 90%, and is similarly The ratio of the chemical form of the oxide or the oxychloride is in the range of 6 〇 to 80%. As in the case of the embodiment, it can be confirmed that under such a configuration, the desired characteristics and effects can be exerted under the war. The present invention includes all of the specific conditions. Although the above description is applied to the case where the roughened surface of the electrolytic copper box is applied, it is of course also applicable to the electrolytic copper crucible to which the glossy surface is subjected to roughening treatment. And the rolled copper drop subjected to the roughening treatment is also the same. If the roughened surface of the electrolyzed mi and the rolled copper box is used, the absolute value of the normal peel strength may be different due to the shape of the roughening treatment and the difference in the surface roughness. However, the heat-resistant peel strength and sulfuric acid and peroxidation may be lowered. The relative deterioration rate of the peel strength after the hydrogen water treatment compared with the normal peeling. In the printed circuit of the present invention, 柘.. „ 丞 用 , , , , , , , , , , , , , , , , , , , , , , , , , , , 最佳 最佳 最佳 最佳 最佳 最佳 最佳 最佳 最佳 最佳 最佳 最佳'And effectively prevent the circuit from invading the surname, so that the sulfuric acid and hydrogen peroxide resistance are stable and stable. Therefore, you should understand the choice of electrolytic copper box and calendered copper box or the choice of coarse 31 201002165. Industrial Applicability As described above, the copper foil for a printed circuit board of the present invention uses a nickel-zinc layer to improve the peeling strength of the resin after the inter-temperature heating is not deteriorated. The heat-resistant peeling strength of the copper foil, in addition to this, it is possible to impart an effect of preventing corrosion of the circuit, and it is possible to make the sulfuric acid-resistant and hydrogen peroxide-resistant cockroaches stable and effective, and in recent years, the micro-patterning of the printed circuit In the development of the frequency, it is applicable to a printed circuit board which is suitable for use as a steel for printed circuit boards, in particular, a copper foil for a packaged substrate, and a steel foil and a resin substrate. A semiconductor package substrate) using a copper-clad laminate. [Drawings briefly described the major elements None None REFERENCE SIGNS 32

Claims (1)

201002165 七、申請專利範圍： 1.-種印刷電路基板用銅箱，係在銅落之粗化面，且備 1鎳與鋅或此等化合物之層(以下’稱為「錄鋅層」），以 該層上，具備鉻酸鹽被膜層，其特徵在於： 、該鎳辞層之每單位面積的鋅附著重量在18〇“—2以 ί/(ΓΓ=,2以下，錄辞層中之錦重量比率{錄附著重 (桌附者重$ +鋅附著重量)}在0 38以上、〇 7以下。 中 上 中 2·如申請專利範圍第&quot;員之印刷電路基板用銅箱，其 該（錄附著重量/(鎳附著重量+鋅附著重量）}在〇·4以 〇·55以下。 3_如申請專利範圍帛1項之印刷電路基板用銅箔，其 該鉻酸鹽被膜層之㈣每單位面積的絡附著重量在％ #g/dm2 以上、10(^g/dm2 以下。 4·如申請專利範㈣财任—項之㈣電路基板 用鋼馆’其中，該鎳辞層所含 t a π 3有之全部鋅中，以辞氧化物 或鋅氫氧化物之形態存在之鋅佔有45〜9〇%。 5. 如申請專利範圍第丨至3項中任—項之印刷電路基板 :鋼羯，其中，該錄辞層所含有之全部鎳中，以錄氧化物 或鎳氫氧化物之形態存在之鎳佔有6〇〜8〇%。 6. 如申as專利範圍第i至3項中任—項之印刷電路基板 鋼箱，其中，在該鉻酸鹽層上，進一步具備石夕烷偶合劑 7 _如申請專利範圍第1 5 至3項中任一項之印刷電路基板 用銅箱，其中’銅羯為電解銅荡，粗化面為電鍍時之粗面、 33 201002165 或是對此粗面進一步施以粗化處理之面、或是對電解鋼箱 之光澤面施以粗化處理之面。 8. 如申請專利範圍第1至3項中任一項之印刷電路基板 用銅箱’其中’銅箔為壓延銅箔，粗化面為對該壓延銅落 施以粗化處理之面。 9. 一種印刷電路基板用覆銅積層板，係將申請專利範圍 第1至8項中任一項之印刷電路基板用銅箔與印刷電路基 板用樹脂基材加以貼合而製成。201002165 VII. Patent application scope: 1. A copper box for printed circuit boards, which is a roughened surface of copper, and is made of nickel and zinc or a layer of these compounds (hereinafter referred to as "zinc recording layer") The layer is provided with a chromate coating layer, wherein: the nickel adhesion layer has a zinc adhesion weight per unit area of 18 〇"-2" in ί/(ΓΓ=, 2 or less, in the layer The weight ratio of the brocade {recording weight (table attached weight $ + zinc attached weight)} is above 0 38, 〇7 or less. In the middle of the middle 2, as in the patent application scope &quot; member of the printed circuit board copper box, The coating weight/(nickel adhesion weight + zinc adhesion weight) is less than or equal to 55. 3_ The copper foil for a printed circuit board according to claim 1, the chromate film (4) The adhesion weight per unit area of the layer is above #g/dm2 and 10 (^g/dm2 or less. 4. If the application for patent (4) is the fiscal-item (4) the steel plate for the circuit board, where the nickel Among all the zinc contained in the layer containing ta π 3 , the zinc present in the form of an oxide or a zinc hydroxide accounts for 45 to 9 % by weight. A printed circuit board according to any one of the items of the third to third aspects of the invention, wherein the nickel contained in the form of oxide or nickel hydroxide is occupied by all of the nickel contained in the recording layer. </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; The copper box for a printed circuit board according to any one of the items 1 to 5, wherein the copper beryllium is electrolytic copper, the roughened surface is a rough surface during plating, 33 201002165 or the rough surface is further roughened The surface of the chemical treatment, or the surface of the electrolytic steel box, which is subjected to a roughening treatment. 8. The copper box for a printed circuit board according to any one of claims 1 to 3, wherein the copper foil is The rolled copper foil is a surface on which the roughened surface is roughened. 9. A copper-clad laminate for a printed circuit board, which is a printed circuit according to any one of claims 1 to 8. The copper foil for a substrate is bonded to a resin substrate for a printed circuit board. 益 34Benefit 34
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